Acylated tetramino-dihaloanthraquinones



United States Patent 3,282,967 ACYLATED TETRAMINO-DIHALO- ANTHRAQUINONESPaul Grossmann, Binningen, Switzerland, assignor to Ciba Limited, Basel,Switzerland No Drawing. Original application May 1, 1962, Ser. No.191,444, now Patent No. 3,234,234, dated Feb. 8, 1966. Divided and thisapplication May 10, 1965, Ser. No.

, 454,733 Claims priority, application Switzerland, May 10, 1961, 5,487/61 4 Claims. (Cl. 260-377) This application is a division of applicationSerial No. 191,444, filed May 1, 1962, now Patent No. 3,234,234.

The present invention provides diacylated1:4:5z8-tetramino-anthraquinones of the formula a,

( HzN IOI N112 Br Br I l AC NH 0 NHAc (2) Ae NH (a NHz I HzN 0 NHAc;

in which A0 represents the radical of an aliphatic carboxylic acid,advantageouslypne containing at most 8 carbon atoms, or the radical of asemi-ester of carbonic acid, Ac represents the radical of an aliphaticcarboxylic acid or the radical of a semi-ester of carbonic acid or theradical of a benzene carboxylic acid or the radical of a benzenesulfonic acid.

The invention also provides a process for the manu facture of the newdyestuffs, wherein anazu-diaminoanthraquinone which contains a halogenatom in ort-hoposition to at least one primary amino group andsubstituents convertible into acylamino groups in para-position to theamino groups, is treated in one or more stages to convert into acylaminogroups the substituents so convertible.

The diamino-anthraquinones used in the process of the inventionadvantageously contain primary amino groups. The starting materials alsocontain halogen atoms, for example, chlorine or especially bromineatoms, in orthoposition to at least one, advantageously to both aminogroups. They also contain a substituent convertible into an acylaminogroup in para-position to each amino group. As such substituents theremay be mentioned more especially halogen atoms, for example, chlorineand especially bromine. the trior tetra-halogenation of 1:5- or1:8-diaminoanthraquinones, for example, 125- or1:8-diamin-o-anthraquinone, by reacting the triortetra-halogen-diaminoanthraquinones with 2 mols of a benzene sulfonamideto form monoor di-halogen-diaminobenzenesulfonylaminoanthraquinones.This reaction is advantageously carried out in an organic solvent, forexample, an aliphatic alcohol, such as butyl, amyl or hexylalcohol,advantageously in the presence of an agent capable of binding acid, suchas alkali metal acetate, alkali metal carbonate or alkaline earth metalcarbonate, and a copper compound, such as copper oxide or coppercarbonate.

One or both of the benzene-sulfonylamide groups in thedisulfonyl-tetra-amino-anthraquinones so obtained may Slch compounds maybe obtained by be hydrolyzed to form the free amino groups, and thelatter may be ac'ylated by reaction with agents capable of introducingthe radical of a carboxylic acid. It the intermediate product containstwo acylatable amino groups, it may be reacted with 2 mols of an agentyielding the radical of an aliphatic monocarboxylic acid or of acarbonic acid semi-ester, or with 1 11101 of an agent yielding theradical of an aliphatic carboxylic acid or of a carbonic acid semi-esterand 1 mol of an agent yielding the radical of a different aliphaticcarboxylic acid or the radical of a carbonic acid semi-ester or theradical of a benzenecarboxylic acid. As acylating agents there are used,for example, formic acid or advantageously the carboxylic acid halides,especially the chlorides of aliphatic or cycloaliphatic carboxylic acidscontaining at most. 8 carbon atoms, for example, of acetic acid, ofpropionic acid, of butyric acid, of valeric acid, of caproic acid or ofcaprylic acid, or cycloaliphatic carboxylic acids, such ashexahydro'benzoic acid, or unsaturated aliphatic carboxylic acids, suchas acrylic acid or crotonic acid, or'substituted carboxylic acids,especially those substituted by halogen atoms, such as chloracetic acidor 'y-chlorobutyric acid and, finally, semi-esters of carbonic acid, forexample, carbonic acid methyl ester or carbonic acid ethyl ester, whichare not stable as such, but their halides are also acylating agents.

Instead of reacting the two acylatable amino groups in succession withdifierent acylating agents, a mixture of the two different acylatingagents may be reacted with the amino-anthraquinone.

The acylation may be carried out by known methods, for example, in aninert medium, such as acetone, nitrobenzene, chlorobenzene, etc., andadvantageously in the presence of a tertiary base, such as pyridine ordimethylaniline. It is of advantage to carry out the reaction at araised temperature.

The new dyestuffs, especially after being suitably pasted, if desired,accompanied, by reprecipitation, for example, from sulfuric acid, arevery suitable for dyeing and printing hydrophobic fibrous materials,especially fibers of polyesters, for example, polyethyleneterephthalates. When applied by the usual dyeing processes, for example,using a dye liquor containing a dispersion of the dyestuff andadvantageously a dispersing agent and dyeing either at temperaturesclose to C., if desired, in the presence of a swelling agent, or underpressure at temperatures above 100 0., they yield pure blue dyeings ofespecially good fastness to light and sublimation.

An important advantage of the dyestuffs of the invention is that theycan be applied from an alkaline bath. This makes them particularlysuitable for application by the so-called thermofix process in which thefabric to be dyed is impregnated advantageously at a temperature notexceeding 60 C. with an aqueous dispersion of the dyestuifadvantageously containing 1 to 50% of urea and a thickening agent,especially sodium alginate, the impregnated fabric being squeezed in thenormal manner. The pressure is advantageously adjusted so that the goodsretain 50 to 100% of their dry weight of dye liquor.

The dyestutf is fixed by subjecting the impregnated fabric to a heattreatment at a temperature above 100 C., for example, at a temperatureranging from to 210 C., it being of advantage to dry the fabric prior tothis treatment, for example, in a current of warm air.

The thermofix process is of special interest for the, dyeing of unionfabrics made of a mixture of polyical bond. Such dyestufis contain, forexample, a chlorotriazine or chlorodiazine radical. In the latter caseit is of advantage to add to the padding liquor an agent capable ofbinding acid, for example, an alkali metal carbonate, alkali metalphosphate, alkali metal borate or alkali metal perborate, or a mixtureof two or more of 135 parts of 1:8-diamino 2:4:5:7tetrabromanthraquinone are heated for 4 hours at the boil in 600 partsof amyl alcohol with 180 parts of para-toluene-sulfonamide, 4.5 parts ofcopper carbonate and 45 parts of potassium acetate. 600 parts ofmethanol are added to the reaction mixture, the latter is then filtered,and the filter residue is washed successively with methanol and waterand dried. There is obtained in good yield 1:8-diamino-2z7-dibromo-4z5-di-(para toluenesulfonamido) anthraquinone. The reactiontakes about 7 hours in the case of the corresponding1:5-diamino-compound.

165 parts of the product so obtained are heated at 40 to 50 C. in'900parts of sulfuric acid of 95% strength until hydrolysis is complete. Thehydrolysis is complete when a test portion no longer gives a colorchange towards green-blue in an organic solvent. The reaction mixture ispoured into ice water, filtered, and the filter radical is washed untilthe washings run neutral, and is then dried. The 1:4:5z8-tetramino 2:7dibromanthraquinone so obtained yields on polyester fibers greenish bluedyeings of excellent fastness to sublimation.

By using 1:8 diamino 2:4:5 :7 tetrachloro anthraquinone, instead of1:8-diamino 224:5 :7 tetrabromanthraquinone, 124:5:8-tetramino -2:7dichloro anthraquinone is likewise obtained in good yield.

By using 1 :5-diamino-2z4:6:8-tetrabromanthraquinone as startingmaterial, there is obtained 1:4:5z8-tetraamino-2 6-dibrom anthraquinone.

63.9 parts of the 1:4:5:8-tetramino 2:7 dibrornanthraquinone obtained asdescribed above are heated for 15 minutes at 100 C. in 225 parts ofnitrobenzene with 39 parts of dimethylaniline, 22.8 parts ofchloro-formic acid ethyl ester and 15 parts of acetyl chloride. To thismixture are added 450 parts of methyl alcohol, the whole is filtered,and the filter residue is washed with methyl alcohol and dried. Theresulting dyestutf of the formula H 1? NH: Br- -Br I CHaCONH O NHCOOCzHlsimilar dyeing properties.

Example 2 42.6 parts of 1:4:5 :8 tetramino 2:7 dibromanthraquinoneobtained as described in Example 1 are heated for about 3 hours at 120C. in 500 parts of chlorobenzene with 13.6 parts of chloroformic acidethyl ester and 13 parts of butyryl chloride. The chlorobenzene isdistilled oil with steam from a neutralized aqueous. suspension. Thedyestuff so obtained, when applied by the thermofix process, dyespolyester fibers reddish blue tints of very good fastness to light,alkali and sublimation.

By using 1:4:5z8-tetramino 2:7 dichloro-anthraquinone or1:4:5:8-tetramino-2:6 dibromanthraquinone as starting material, thereare obtained dyestuffs having similar dyeing properties.

By using an equimolecular proportion of chloroformic acid methylesterinstead of the ethyl ester a dyestuff is obtained which dyes polyesterfibers similar shades.

By using an equimolecular proportion of benzoyl chloride, instead ofbutyryl chloride, there is obtained a dyestufr" yielding a somewhat moregreenish dyestulf.

By using 1:8-dirnethy1amino 4:5 diamino 2:7 dibromanthraquinone asstarting material there is obtained a dyestutl yielding a somewhat morereddish tint.

Example 3 parts of 1:4:5z8-tetramino 2:7 dibromanthraquinone are heatedfor 1 hour at 60 C. in 5 00 parts of dimethylaniline with 27.2 parts ofchloro-formic acid ethyl ester and 17 parts of acetyl chloride. Thereaction mixture is poured into 5000 parts of a mixture ofice-waterExample 4 4 parts of 1:4:5:S-tetramino-Z:7-dibromanthraquinone areheated for 3 hours at the boil in .40 parts of formic acid. The dyestuflso obtained is precipitated by the addition of 40 parts of water. Itdyes polyester fibers blue tints possessing very good properties offastness.

Example 5 36.7 parts ofl:8-diamino-2:7-dibrorno-4:5-di=(paratoluene-sulfamido)-anthraquinone,obtained as described in the first paragraph of Example 1, areintroduced at 0 to 5 C., into 300 parts by volume. of sulfuric acid of80% strength, and the whole is stirred for 5 hours at that temperature.The reaction mixture is poured into ice water and filtered. The filterresidue is washed until the washings run neutral, and is then dried.There are obtained about 28.45 parts of1:4:8-triamino-2:7-dibrorno-S-paratoluene-sulfonamidoanthraquinone.

The product so obtained is heated for 15 minutes at C. in 300 parts byvolume of dimethylaniline with 5 parts of acetyl chloride; The reactionmixture is poured into 1000 parts of a mixture of ice water and 100parts of concentrated sulfuric acid, the whole is filtered, and thefilter residue is washed until the washings run neutral. The dyestulf soobtained, when applied by the high-temperature or thermofix process,dyes polyester fibers blue tints of excellent fastness to light, alkaliand sublimation.

Example 6 1 part of an aqueous paste of the dyestuif of the formula BrBr I II O aCONH O NHCOO OIHI is ground with approximately 1 part ofdried sulfite ce1lulose waste liquor in a roller mill to a fine pastehaving a dyestufi content of about 100 parts'of a fibrous material ofpolyethylene terephthalate are washed for half an hour in a bathcontaining, per 1000 parts of water, 1 to 2 parts of the sodium salt ofN- benzyl- -heptadecylbenzimidazole disulfonic acid and 1 part of aconcentrated aqueous solution of ammonia. The material is then enteredinto a dyebath of 3000 parts of Water in which the dyestulf pasteobtained as described in paragraph 1 has been dispersed in the presenceof 4 parts of the sodium salt of N-benzyl-nheptadecylbenzimidazoledisulfonic acid. The whole is heated to 130 C. in a pressure vessel andmaintained at that temperature for about 1 hour. The material is thenwell rinsed and, if necessary, washed for half an hour at 60 to 80 C.with a solution containing, per 1000 parts of water, 1 part of thesodium salt of N-benzyl-p-heptadecylbenzimidazole disulfonic acid. Thereis obtained a blue dyeing of excellent fastness to sublimation andlight.

Example 7 14 parts of the dyestuif used in Example 6 are finely groundin a ball mill with 126 parts of a neutral solution of 125 parts ofdinaphthylmethane disulfonic acid in 1000 parts of water.

A padding liquor is prepared from the following com- 7 ponents 200 partsof the dyestutf paste described above 300 parts of sodium alginate(1:100) 500 parts of water 1000 parts A polyester fabric is padded withthe above padding liquor in such a manner as to increase its weight by50 to 60%. It is then dried at 60 C. The fabric is then subjected to aheat'treatment for 15 to 120 seconds at 200 to 220 C. It is then soapedfor minutes at the boil in a solution of 5 grams of soap in 1 liter ofwater, and is then further treated in the usual manner (rinsing,drying). There is obtained a strong blue dyeing of excellent fastness tolight and sublimation.

What is claimed is:

1. The dyestuff of the formula HgN (M) NH: Brwlh l I CHsCONH O NHC O 002115 2. The dyestuif of the formula HzN o lTIH2 Br Br CHaCHzCHzCONH ANHCOOOzHa 3. The dyestuff of the formula HqN O NH: I!

I GHzQHECHflCONH O NHCOOCzHs 4. The dyestuff of the formula H N El) NH:

Br Br 1 CzHsOOCNH 0 I IHCOOChHa References Cited by the Examiner UNITEDSTATES PATENTS 2,063,027 12/1936 Buxbaum 260377 X 2,063,028 12/1936Buxbaum et a1. 260377 X LORRAINE A. WEINBERGER, Primary Examiner.

H. C. WEGNER, Assistant Examiner.

1. THE DYESTUFF OF THE FORMULA1,8-DI(NH2-),2,7-DI(BR-),4-(C2H5-O-CO-NH-),5-(CH3-CO-NH-) ANTHRAQUINONE